Process for the manufacture of amino and nitro derivatives



Patented June 15, 1937 PROCESS FOR THE MANUFACTURE AMINO AND NITRO- DERIVATIVES Pierre Petitcolas, Rouen, France, assignor to Compagnie Nationale de Matieres Colorantes et Manufactures de Produits Chimiques du Reunies, Etablissements Kuhlmann,

Paris, France, a corporation of France No Drawing. Application March 19, 1937, Serial No. 131,933. In France March 5, 1936 2 Claims.

In the French Patent No. 720,559 of the 24th July, 1931, there has been described a process for the preparation of azodyestuffs consisting inter alia in coupling with arylides of p-hydroxynaphthoic acid diazo compounds of aromatic amines of formula:

in which R represents a halogen atom and R any group. The amines in question may be obtained by reduction of nitro compounds of the formula:

blTH-CO-R Now it has been found, according to the present invention, that the above nitro and halogen compounds may readily be condensed with salts of phenolic compounds giving products of the general formula:

in which R has the same significance as above, and R and R" indicate substituted or unsubstituted aryl groups. These products themselves give by subsequent reduction aromatic amines of the formula:

lTIH-OO-R l NHa which are capable of being diazotized and coupled in substance or on the vegetable fibre with coupling compounds of substantive character, giving in particular a range of dyeings from Bordeaux to violet, whose properties of fastness and brightness are improved over those of the'dyeings described in French Patent No. 720,559 mentioned above.

The nitro and halogen compounds of formula:

IIIH-CO-R may be readily obtained by acylation of the bases derived from ortho-amino-diphenyloxide, having in para-position to the oxygen link a halogen atom in the aryl group carrying the amino group, and then by nitration of the acyl amino compounds thus obtained. This nitration may advantageously be effected by means of concentrated nitric acid, either alone or with the addition of a solvent, such as chloro-benzene, acetic acid, etc.

The condensation of these products with the phenolic compounds is preferably effected by employing them in the form of their alkali salts and operating in the presence of an excess of phenolic compound in the free state. The reduction of the condensation products may take place according to the usual processes.

The possibility of employing certain of the amines obtained according to the process of the invention has already been mentioned. This is the case in particular for those in which R in the formula represents the residue of an at least partially hydrogenated cyclic hydrocarbon. However, such amines have not yet been described and no convenient process has yet been proposed for their preparation. I

The following are non-limiting examples illustrating the carrying of the invention into effect:--

Example 1 small pale yellow crystals; it is constituted by 2- N benzoylamino-l-chloro-5-nitro-diphenylether.

On the other hand, 17 grams of pure caustic potash are dissolved in 150 grams of phenol at about -120 C. The temperature is gently raised to 185 C. in order to remove all the water formed in the reaction. After cooling to C. 92 grams of 2benzoylamino-4-chloro-5-nitrodiphenylether are added gradually and the whole is heated for 8 hours at 150 C. The mass is poured into water, rendered alkaline with caustic soda to eliminate the excess phenol and, after filtration of the crystallizedcondensationproduct, it is purified with acetic acid. This product has the form of yellow crystals (M. P. 201-202 0.).

By reduction by one of the usual processes, the diphenylether of 2-benzoylamino-5-aminohydroquinone, of melting point 121 C. is isolated.

The diazonium salt of this product may be isolated in the following manner:-

40 grams of diphenylether of 2-benzoylamino- 5-aminohydroquin0ne are pasted for a few hours in 100 cos. of concentrated hydrochloric acid of 21 Be. to which has been added 10 cos. of water. 10 grams of dry sodium nitrite are gradually added while agitating energetically. After 2 hours of agitation the diazonium chloride is filtered, which has the form of fine yellow crystals. The crystals are pressed and dried by admixture with dehydrated aluminium sulphate. The product may be employed for example by a simple solution in water for the production of azo dyes.

Example 2 150 grams of para-cresol have added thereto 18 grams of pure potash. The mixture is heated to 190-195 C. to eliminate the water formed in the reaction, and then is allowed to cool to about 150 C. 92 grams of 2-benzoylamino-4-chlorofi-nitro-diphenylether, prepared as in Example 1, is introduced. The whole is heated for 5 hours to -180 C. The mass is poured into alkaline water. The condensation product which has crystallized gradually is purified with acetic acid (M. P. 182 (3.).

By reduction according tothe usual processes the 2-amino-3-(4-methyl) -phenoxy-5-benzoylamino-G-phenoxy-benzene of formula:

.CHz

and the point of fusion of which, after recrystallization from alcohol, is 119 C.

Example 3 A mixture of 150 grams of ortho-cresol and 12.5 grams of caustic potash is heated at 180-190 C. so as to distill off the water formed in the reaction.

After cooling to 120 80 grams of 2-chloro-2 benzoylamino-4-ch1oro-5-nitro-dipl1enylether is added and the whole is heated to 140 for an hour. The product is poured into water rendered alkaline with caustic soda and is recrystallized from alcohol. A nitro compound of M. P. 193-194" is obtained. The product is reduced with iron and acetic acid in the usual manner and the iron sludge is extracted with boiling ethyl alcohol. The base isolated melts at 67-68; it has the formula:

llqHz CH3 Emample 4 In the same way there can be obtained:

(1) 2-benzoylamino4-ortho-tolyloxy-5-nitror diphenylether of melting point -176 which, when reduced, gives the base:

NH-C O of melting point 88-89".

(2) 2'chloro-2 benzoylamino 4-phenoxy-5- nitro-diphenylether of melting point 176 which, by reduction, gives the base:

of melting point 122-123.

(3) 2-benzoylamino-4-ortho-chloro-phenoxy- 5-nitro-diphenylether of melting point 178-179 which, when reduced, gives the base:

IIIH: (I31 QO-C team of melting point 95-96.

(44) 2-chloro-2-benzoylamino-4-ortho-chlor0- phenoxy-5-nitro-diphenylether, of melting point 188-189 which, when reduced, gives the base:

2 grams of the a-naphthylamide of 2.3-hydroxynaphthoic acid are pasted with 2.5 cos. of denatured alcohol and 1.4 cos. of caustic soda of 34 B. It is diluted with 3 cos. of cold water and a clear solution is obtained to which is added 1 cc.. of formaldehyde of 33% strength.

again rinsed and dried.

nents of substantive character:-

A violet-reddish shade is obtained.

The following table gives the shades of dyes obtained by coupling the diazo derivatives of the bases described with different coupling comp'ofor half anhouratthe boil in .a bath containing grams of Marseilles soap per litre and. then Diazo compound Coupling compound Shade 2-benzoylamino -4-o-tolyloxy-fi-amino-diphenylether Diacetoacetyl-o-toluidine Yellowl Do Anilide of 2.3-hydroxy-naphthoicac Borgeaux-oorint m-Nitranilide of 2,3-hydroxy-naphthoic acid. Bordeaux. fl-Naphthylamide oi 2,3-hydroxy-naphthoic ac o. 5-Oli1oro-o-toluidide of 2,3-hydroxy-naphthoic ac B o rtdl e a u x cor- 111 p-Anisidide Bordeaux. o-Toluidide o. a-Naphthylamide- Corinth. o-An 1d Bordeaux.

id e p-Ohloro-o-anisidide-.- B-Hydroxynaphthoyl-l-amino-B-chloro- 4,6 -dimethoxybenzene Diacetoacetyl-o-toluidine Anilide of 2.3-hydroxy-naphthoic acid m-Nitranilide of 2,3-hydroxy-naphthoic acid- B-Naphthylamide of 2,3-hydroxy-naphthoic acidfi-Chlpro o-toluidide of 2,3-hydroxy-naphthoic acid o-Anisidide p- Chloro-o-anisidide 6-Hydroxynaphthoyl-l-amino-K-chloro-4,6 dimethoxybenzene.

Diacetoacetyl-o-toluidine Anilide of 2,3-hydroxy-naphthoic acid m-Nitranilide of 2,3-hydroxy-naphthoicacid fi-Naphthylamide oi 2,3-hydroxy-naphthoic aoid.. S-Chloro-o-toluidide of 2,3-hydroxy-naphthoic acid p-Anisidide o-Toluidide a-Naphthylamide o-Anisidide p-Ch10ro-0-anisidide B-Hydroxynaphthylamino-ii-chloro-4,6-dimethoxy-benzene. Diacetoacetyl-o-toluidine Anilide of 2,3-hydroxynaphthoic acid m-Nitranilide oi 2,3-hydroxy-naphthoic acid fi-Naphthylamide of 2,3-hydroxy-naphthoic ac 5-Chloro-o-toluidide of 2 3-hydroxy-naphthoic acid p-Anisidide. o-Toluidide a-Naphthylam o-Anisidide p-Chloro-o-anisidi B-Hydroxynaphthoy benzene. Diacetoacetyl-o-toluidine Anilide of 2,3-hydroxynaphthoio a m-Nitranilide of 2,3-hydroxy-naphthoic acid fi-Naphthylamide of 2,3-hydroxy-naphthoic acid 5-Ch1oro-o-to1uidide of 2,3-hydroxy-naphthoic acid no-3-chloro-4fi-dimethoiry idlde p-Ohloro-o-anisidide fl-Hydroxynaphthoyl amino-3-chloro-4,

benzene. Diacetoacetyl-o-tolu1dine Anilide of 2,3-hydroxynaphthoic acid m-Nitranilide of 2,3-hydroxy-naphthoic acid. B-Naphthylamide of 2,3-hydroxy-naphthoic acid 5-Chloro-o-to1uidide of 2,3-hydroxy-naphthoic acid p-Anisidide o-Toluidide.

wNaphthylamide o-Anisidide ether.

p-Chloro-o-anisidide fl-H y d r o x ynaphthoyl-l-a m i n o-3-chloro 4,6-dimethoxybenzene.

of the diazo derivative of the produt of Example 1 and 40 grams of sodium chloride in 1 litre of water The duration of the development is half an hour in the cold. Then the skein of cotton is rinsed, acidified, and again rinsed and soaked fastness to chlorine, boiling under air and to light.

I claim:

Bordeaux-corinth.

inth do. do.

Yellow. Bordeaux. Reddish-brown. Bordeaux.

do. Bordeaux-corinth. Bordeaux. do.

Bordeaux.

Corinth.

Bordeaux. do. do.

do. Bordeaux-corinth. Bordeaux.

do. do.

Yellow.

Corinth.

Violet.

Corinth. Bordeaux-coro. Corinth. Bordieaux.

The shades thus obtained have a remarkable pressure, to

1. A process for the manufacture of nitro compounds and amines comprising condensing a nitrated and halogenated product of the general formula IIIH- C 0' 00115 R'OC Halogen where R represents an aryl radical taken from the group consisting of phenyl and chloro-phenyl, with an alkali metal salt of a compound taken from the group consisting of phenols, chlorophenols and cresols.

2. In a process for the manufacture of nitro 15 compounds and amines the steps consisting in condensing a nitrated and halogenated product of the general formula where R represents an aryl radical taken from the group consisting of phenyl and chloro-phenyl, With an alkali metal salt of a. compound taken from the group consisting of phenols, chlorophenols and cresols, and in reducing the condensation product obtained.

PIERRE PETITCOLAS. 

